CN106634688B - A kind of thermosetting property oxidation modification Cassava starch adhesive and preparation method thereof - Google Patents
A kind of thermosetting property oxidation modification Cassava starch adhesive and preparation method thereof Download PDFInfo
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- CN106634688B CN106634688B CN201710001278.4A CN201710001278A CN106634688B CN 106634688 B CN106634688 B CN 106634688B CN 201710001278 A CN201710001278 A CN 201710001278A CN 106634688 B CN106634688 B CN 106634688B
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- cassava starch
- oxidation modification
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
- C09J103/04—Starch derivatives
- C09J103/10—Oxidised starch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/18—Oxidised starch
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Materials Engineering (AREA)
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a kind of thermosetting property oxidation modification Cassava starch adhesives and preparation method thereof, the thermosetting property oxidation modification Cassava starch adhesive is prepared by oxidation modification Cassava starch adhesive, flour, isocyanates, carboxylic acrylonitrile butadiene rubber latex, and the oxidation modification Cassava starch adhesive is prepared by PVA, tapioca, SDS, NaClO.Specific preparation process is as follows：(1) tapioca breast is added into PVA solution, stirs evenly, waits being warming up to 30~50 DEG C, regulation system pH is alkalescent, and SDS emulsifying solns are added；(2) regulation system pH is 9~11, dropwise addition oxidant NaClO, up to oxidation modification Cassava starch adhesive after oxidation reaction；(3) flour, isocyanates and carboxylic acrylonitrile butadiene rubber latex are added into oxidation modification Cassava starch adhesive, is uniformly mixing to obtain thermosetting property oxidation modification Cassava starch adhesive.The method is simple for process, time-consuming short, at low cost, and the function admirable of prepared Cassava starch adhesive.
Description
Technical field
The invention belongs to wood adhesive technical fields, and in particular to a kind of Cassava starch adhesive and preparation method thereof.
Background technology
The adhesive generally used in timber industry at present is synthesis macromolecule adhesive, and raw material is both from can not
Regenerated fossil resources.With petering out for fossil resources and being increasingly enhanced for people's environmental consciousness, exploitation is renewable, green
The wood adhesive of environmental protection has become the active demand of timber industry.Starch is that one kind is cheap, derives from a wealth of sources, is environmentally protective
Natural macromolecular material, have the characteristics that nontoxic, pollution-free.If with Starch Fraction or all substitution fossil resources synthesis
High molecular material, be applied to wood adhesive, it will great facilitation is played to adhesive industry and starch industry.Cause
This, in recent years, starch adhesive is constantly of interest by numerous scholars as a kind of green environment friendly adhesive.Wood
Since its amylopectin content is high, tack is big etc., characteristics have great advantage sweet potato starch in adhesive producing field tool.
Oxidation modification is to prepare the most common means of Modified Oxidize Starth Adhesive stick, a large amount of in starch molecule after oxidation
Hydrophilic group hydroxy is transformed into carboxyl or carbonyl, it is easier to react, while macromolecular chain is broken, mobility improves.It prepares
The common oxidant of oxidized tapioca adhesive has KMnO4、H2O2And NaClO.The oxidation of NaClO occurs mainly in starch
C in molecule2、C3Secondary hydroxyl on, compared with other oxidants, NaClO oxidations not only occur on amorphous region in starch, and
And intramolecule is also penetrated into, oxidation effectiveness is preferable, selects it as oxidant then.The preparation of oxidation modification starch adhesive at present
Technics comparing is cumbersome, and cost is higher, and the performance of gained adhesive is also poor, cannot meet plywood applications requirement.Therefore it makes
Standby simple for process, at low cost, function admirable adhesive becomes very necessary.
Invention content
In order to overcome water resistance that is in the prior art insufficient and being effectively improved glued board, the present invention provides a kind of anti-
Thermosetting property oxidation modification Cassava starch adhesive and preparation method thereof short, easy to operate between seasonable, to be suitable for industrial applications.
The purpose of the present invention is what is be achieved through the following technical solutions：
A kind of thermosetting property oxidation modification Cassava starch adhesive, in terms of parts by weight, by 40~50 parts by weight oxidation modifications
Cassava starch adhesive, 3~5 parts by weight flour, 4~6 parts by weight isocyanates, 3~5 parts by weight carboxylic acrylonitrile butadiene rubber latexes prepare and
At, wherein：The oxidation modification Cassava starch adhesive is by 5.6~8 parts of PVA, 70~100 portions of tapiocas, 2~5 parts of SDS, 5
~15 parts of NaClO are prepared.
A kind of preparation method of above-mentioned thermosetting property oxidation modification Cassava starch adhesive, includes the following steps：
(1) tapioca breast is added into PVA solution, stirs evenly, waits being warming up to 30~50 DEG C, NaOH solution tune is added
Section system pH is alkalescent, and SDS solution is added, and is emulsified 0.5~1 hour.
(2) NaOH solution is added dropwise, regulation system pH is 9~11, and oxidant NaClO is added dropwise, after oxidation reaction discharging to get
Oxidation modification Cassava starch adhesive.
(3) oxidation modification Cassava starch adhesive made above is taken, flour, isocyanates and carboxyl butyronitrile glue is added
Breast is uniformly mixing to obtain thermosetting property oxidation modification starch adhesive.
In the present invention, the PVA is RS-2117, RS-1717, RS-1788 or RS-1799.
In the present invention, a concentration of 10~20wt% of the PVA solution.
In the present invention, a concentration of 35~45wt% of the tapioca breast.
In the present invention, the oxidizing reaction temperature is 40~50 DEG C, and the time is 40min~2h.
In the present invention, the thermosetting property oxidation modification Cassava starch adhesive when glued board is glued in use, be added face
Powder, isocyanates and carboxylic acrylonitrile butadiene rubber latex, the respectively assembly under preformer and hot press.
The present invention uses NaClO oxidation modification Cassava starch adhesives, the macromolecular chain of starch to be destroyed, and mobility becomes
It is good, and reduce rise and meet again.PVA is added as continuous phase, starch granules can be wrapped, plays the role of protection thickening,
SDS emulsifications are added, makes the mixing of starch glue system evenly, delays to be layered.When sizing be added isocyanates as crosslinking agent with
And curing agent, and carboxylic acrylonitrile butadiene rubber latex is added and is blended with amylan, both substances all contain unsaturated group, reactivity
Height, high temperature under pressure can with the active group in starch and plank occur it is violent react, form firm chemical bond,
Improve bonding strength.The method is simple for process, time-consuming short, at low cost, and the function admirable of prepared starch adhesive.Using this
Method can effectively improve the bonding strength and water resistance of starch adhesive.
The chemical equation of oxidized tapioca reaction process is as follows：
Compared with prior art, the present invention has the following advantages：
(1) the Cassava starch adhesive transparency obtained by the present invention is high, and modest viscosity is conducive to storage-stable.
(2) Cassava starch adhesive preparation process produced by the present invention is simple to operation, takes short.
(3) Cassava starch adhesive water resistance produced by the present invention is excellent, and bonding strength is obviously improved
(4) present invention preparation reaction temperature is low, and postprocessing working procedures are simple, greatly reduce oxidation modification tapioca gluing
The producting process difficulty of agent, it is easy to accomplish industrialized production.
Specific implementation mode
Technical scheme of the present invention is further described with reference to embodiment, however, it is not limited to this, every right
Technical solution of the present invention is modified or replaced equivalently, and without departing from the spirit of the technical scheme of the invention and range, should all be contained
It covers in protection scope of the present invention.
Embodiment 1
A kind of preparation method of thermosetting property oxidation modification Cassava starch adhesive is present embodiments provided, specific steps are such as
Under：
(1) PVA (RS-1717) of 6.4 parts by weight is dissolved in the deionized water of 36.3 parts by weight and is made into the molten of 15wt%
Liquid is placed in the reaction kettle with blender, is warming up to 90 DEG C and is dissolved to PVA, is then cooled to 40 DEG C.
(2) tapioca of 80 parts by weight is dissolved in the deionized water of 124.5 parts by weight, is made into the starch of 39.1wt%
Breast is added in the PVA solution that step (1) is configured, and waits for that reaction kettle water temperature rises to 40 DEG C, NaOH solution regulation system pH is added dropwise
=8, the SDS solution of 20.2 parts by weight 10wt% is then added, keeps the temperature 30min.
(3) NaOH solution regulation system pH=9 is added dropwise, the NaClO solution of 5 parts by weight is then added dropwise, 30min is dripped
At the process is 9 by the way that HCl solution regulation system pH is added dropwise, and 40min is kept the temperature after being added dropwise to complete, and is discharged up to oxidation modification wood
Sweet potato starch adhesive.
(4) it takes the oxidation modification Cassava starch adhesive that 45 parts by weight are made above, is added the flour of 4.5 parts by weight, 5.4
The isocyanates of parts by weight and 4 parts by weight carboxylic acrylonitrile butadiene rubber latexes, are uniformly mixing to obtain thermosetting property oxidation modification Tapioca adhesive
Stick.
The thermosetting property oxidation modification Cassava starch adhesive that the present embodiment obtains is detected and glued board is suppressed,
The results are shown in Table 1.
Embodiment 2
A kind of preparation method of thermosetting property oxidation modification Cassava starch adhesive is present embodiments provided, specific steps are such as
Under：
(1) PVA (RS-1717) of 7.2 parts by weight is dissolved in the deionized water of 40.9 parts by weight and is made into the molten of 15wt%
Liquid is placed in the reaction kettle with blender, is warming up to 90 DEG C and is dissolved to PVA, is then cooled to 40 DEG C.
(2) tapioca of 90 parts by weight is dissolved in the deionized water of 139.6 parts by weight, is made into the starch of 39.2wt%
Breast is added in the PVA solution that step (1) is configured, and waits for that reaction kettle water temperature rises to 40 DEG C, and NaOH solution adjustment system pH is added dropwise
=8.2, be then added 35.1 parts by weight, 10wt% SDS solution, keep the temperature 30min.
(3) NaOH solution regulation system pH=10 is added dropwise, the NaClO solution of 10 parts by weight is then added dropwise, 30min is dripped
At the process is 10 by the way that HCl solution regulation system pH is added dropwise, and 2h is kept the temperature after being added dropwise to complete, and is discharged up to oxidation modification cassava
Starch adhesive.
(4) it takes the oxidation modification Cassava starch adhesive that 45 parts by weight are made above, is added the flour of 4.5 parts by weight, 5.4
The carboxylic acrylonitrile butadiene rubber latex of the isocyanates of parts by weight and 4 parts by weight is uniformly mixing to obtain thermosetting property oxidation modification tapioca
Adhesive.
The thermosetting property oxidation modification Cassava starch adhesive that the present embodiment obtains is detected and glued board is suppressed,
The results are shown in Table 1.
Embodiment 3
A kind of preparation method of thermosetting property oxidation modification Cassava starch adhesive is present embodiments provided, specific steps are such as
Under：
(1) PVA (RS-1717) of 8 parts by weight is dissolved in the solution that 15wt% is made into the deionized water of 45.7 parts by weight,
It is placed in the reaction kettle with blender, is warming up to 90 DEG C and is dissolved to PVA, be then cooled to 40 DEG C.
(2) tapioca of 100 parts by weight is dissolved in the going in example water of 155 parts by weight, is made into the starch of 39.2wt%
Breast is added in the PVA solution that step (1) is configured, and waits for that reaction kettle water temperature rises to 40 DEG C, NaOH solution regulation system pH is added dropwise
=7.97, be then added 50 parts by weight, 10wt% SDS solution, keep the temperature 30min.
(3) NaOH solution regulation system pH=11 is added dropwise, the NaClO solution of 15 parts by weight, 30min is added to be added dropwise to complete, it should
Process is 11 by the way that HCl solution regulation system pH is added dropwise, and 1.5h is kept the temperature after being added dropwise to complete, and is discharged up to oxidation modification tapioca
Adhesive.
(4) it takes the oxidation modification Cassava starch adhesive that 45 parts by weight are made above, is added the flour of 4.5 parts by weight, 5.4
The isocyanates of parts by weight and the carboxylic acrylonitrile butadiene rubber latex that 4 parts by weight are added, are uniformly mixing to obtain thermosetting property oxidation modification cassava
Starch adhesive.
The thermosetting property oxidation modification Cassava starch adhesive that the present embodiment obtains is detected and glued board is suppressed,
The results are shown in Table 1.
The performance test of 1 thermosetting property oxidation modification Cassava starch adhesive of table
| Title | Solid content (%) | Viscosity (mPas) | Wet shape bonding strength (MPa) |
| The adhesive of embodiment 1 | 28.4 | 234.5 | 0.89 |
| The adhesive of embodiment 2 | 22.67 | 104.5 | 0.97 |
| The adhesive of embodiment 3 | 22.6 | 211.5 | 1.10 |
In the above test, the test reference of prepared oxidation modification Cassava starch adhesive viscosity and solid content
GBT-14074-2006《Wood adhesive and its resin method of inspection》, wet shape bonding strength is with reference to GB/T 9846-88《It is glued
The measurement of plate intensity》, 3h will be impregnated in the water of the glued board immersion (63 ± 3) DEG C of the adhesive compacting in table 1, is surveyed under hygrometric state
It has a try part tensile shear strength.
Embodiment 4
The present embodiment is unlike embodiment 1-3：The PVA is RS-2117.
Embodiment 5
The present embodiment is unlike embodiment 1-3：The PVA is 1788.
Embodiment 6
The present embodiment is unlike embodiment 1-5：A concentration of 12wt% of the PVA solution, starch milk it is a concentration of
36wt%.
Embodiment 7
The present embodiment is unlike embodiment 1-5：A concentration of 18wt% of the PVA solution, starch milk it is a concentration of
42wt%.
Embodiment 8
The present embodiment is unlike embodiment 1-7：The thermosetting property oxidation modification Cassava starch adhesive is by 42 weight
Part oxidation modification starch adhesive, 3.5 parts by weight flour, 4.5 parts by weight isocyanates, 3.5 parts by weight carboxylic acrylonitrile butadiene rubber latex systems
It is standby to form.
Embodiment 9
The present embodiment is unlike embodiment 1-7：The thermosetting property oxidation modification Cassava starch adhesive is by 48 weight
Part oxidation modification starch adhesive, 4.0 parts by weight flour, 5.0 parts by weight isocyanates, 4.5 parts by weight carboxylic acrylonitrile butadiene rubber latex systems
It is standby to form.
Claims (6)
1. a kind of thermosetting property oxidation modification Cassava starch adhesive, it is characterised in that the thermosetting property oxidation modification Tapioca adhesive
Stick is in terms of parts by weight, by 40~50 parts by weight oxidation modification Cassava starch adhesives, 3~5 parts by weight flour, 4~6 weight
Part isocyanates, 3~5 parts by weight carboxylic acrylonitrile butadiene rubber latexes are prepared, and the oxidation modification Cassava starch adhesive is by 5.6~8
Part PVA, 70~100 portions of tapiocas, 2~5 parts of SDS, 5~15 parts of NaClO are prepared, the thermosetting property oxidation modification cassava
Starch adhesive is in use, flour, isocyanates and carboxylic acrylonitrile butadiene rubber latex are added when glued board is glued, respectively in preformer
With assembly under hot press.
2. thermosetting property oxidation modification Cassava starch adhesive according to claim 1, it is characterised in that the PVA is RS-
2117, RS-1717, RS-1788 or RS-1799.
3. a kind of preparation method of thermosetting property oxidation modification Cassava starch adhesive as claimed in claim 1 or 2, it is characterised in that
Steps are as follows for the method：
(1) tapioca breast is added into PVA solution, stirs evenly, waits being warming up to 30~50 DEG C, NaOH solution is added and adjusts body
Be pH be alkalescent, be added SDS solution, emulsify 0.5~1 hour；
(2) NaOH solution is added dropwise, regulation system pH is 9~11, and oxidant NaClO is added dropwise, and discharging is to get oxidation after oxidation reaction
Modified Oxidize Starth Adhesive stick；
(3) oxidation modification Cassava starch adhesive made above is taken, flour, isocyanates and carboxylic acrylonitrile butadiene rubber latex is added,
It is uniformly mixing to obtain thermosetting property oxidation modification Cassava starch adhesive.
4. the preparation method of thermosetting property oxidation modification Cassava starch adhesive according to claim 3, it is characterised in that institute
State a concentration of 10~20wt% of PVA solution.
5. the preparation method of thermosetting property oxidation modification Cassava starch adhesive according to claim 3, it is characterised in that institute
State a concentration of 35~45wt% of tapioca breast.
6. the preparation method of thermosetting property oxidation modification Cassava starch adhesive according to claim 3, it is characterised in that institute
It is 40~50 DEG C to state oxidizing reaction temperature, and the time is 40min~2h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| SE545882C2 (en) * | 2021-12-29 | 2024-03-05 | Nicolas Neitzel | An adhesive composition for wood panel composites |
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| CN111690189B (en) * | 2020-06-12 | 2021-05-14 | 华南理工大学 | Carboxyl nitrile rubber/carboxyl starch composite material and preparation method and application thereof |
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| CN1884414A (en) * | 2005-06-25 | 2006-12-27 | 德华兔宝宝装饰新材股份有限公司 | Aldehyde-free cement for wood-based panel |
| US8147979B2 (en) * | 2005-07-01 | 2012-04-03 | Akzo Nobel Coatings International B.V. | Adhesive system and method |
| CN103013379A (en) * | 2013-01-21 | 2013-04-03 | 黑龙江佰嘉生物质材料有限公司 | Water-resistant starch adhesive for wood adhesion and preparation method of water-resistant starch adhesive |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| SE545882C2 (en) * | 2021-12-29 | 2024-03-05 | Nicolas Neitzel | An adhesive composition for wood panel composites |
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